The best method is Electrochemical Impedance Spectroscopy. But you must have to high impedance set-up. You can use also standard method described in ISO and ASTM standards.
The protective property of any coating systems is strongly related to its integrity as this coating performed as protective, chemically stable, compact, defects free, coherent, and adherent to the substrate and, have excellent electrical resistance. Subsequently, such coating is revealing an excellent barrier against the transport of aggressive species from the environment to get in direct contact with the underlying steel surface by different paths. In general, this mean that coatings physical integrity is as important as its chemical barrier properties and the sum of these properties defines the integrity level of coatings throughout the phases of the laboratory test, field test and the real service life. Therefore, the long term immersion for OCP investigation is essential test telling you how the coating protective property changed throughout the test. The changes in the coating protective properties can be follow and monitor by suitable available technical routs including the electrochemical impedance spectroscopy, electrochemical noise measurement or tafel scan plot.